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131.
A micromethod for the quantitative analysis of caffeine present in small quantities (100 microliter) of whole blood is described. It is based on the gas chromatographic--mass spectrometric analysis of chloroform extracts of biological samples. The method is relatively simple, rapid, specific and sensitive; as little as 20 ng of caffeine can be measured. 相似文献
132.
Soyoung Kim Bao-Ning Su Soedarsono Riswan Leonardus B.S. Kardono Johar J. Afriastini Judith C. Gallucci Heebyung Chai Norman R. Farnsworth Geoffrey A. Cordell Steven M. Swanson A. Douglas Kinghorn 《Tetrahedron letters》2005,46(52):9021-9024
Two benzo[b]oxepine derivatives, edulisones A (1) and B (2), were isolated from the bark of Aglaia edulis, collected in Indonesia. The relative stereochemistry of 1 was determined by single-crystal X-ray diffraction analysis. Treatment of compounds 1 and 2 with lithium hydroxide produced the same hydrolysis products, 1a and 1b, as a result of cleavage of the pyrrolidine ring to an alkylated amide mixture in each case, which demonstrated that these substances are epimeric at their 2-aminopyrrolidine moiety. 相似文献
133.
Ronald E. Hostetler John W. Swanson 《Journal of polymer science. Part A, Polymer chemistry》1974,12(1):29-43
The polyethyleneimine (PEI)–water–silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI–cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state. 相似文献
134.
Banerjee AL Swanson M Roy BC Jia X Haldar MK Mallik S Srivastava DK 《Journal of the American Chemical Society》2004,126(35):10875-10883
We elaborate on a novel strategy for enhancing the binding affinity of an active-site directed inhibitor by attaching a tether group, designed to interact with the surface-exposed histidine residue(s) of enzymes. In this approach, we have utilized the recombinant form of human carbonic anhydrase-II (hCA-II) as the enzyme source and benzenesulfonamide and its derivatives as inhibitors. The steady-state kinetic and the ligand binding data revealed that the attachment of iminodiacetate (IDA)-Cu(2+) to benzenesulfonamide (via a triethylene glycol spacer) enhanced its binding affinity for hCA-II by about 40-fold. No energetic contribution of either IDA or triethylene glycol spacer was found (at least in the ground state of the enzyme-inhibitor complex) when Cu(2+) was stripped off from the tether group-conjugated sulfonamide derivative. Arguments are presented that the overall strategy of enhancing the binding affinities of known inhibitors by attaching the IDA-Cu(2+) groups to interact with the surface-exposed histidine residues will find a general application in designing the isozyme-specific inhibitors as potential drugs. 相似文献
135.
Roy BC Banerjee AL Swanson M Jia XG Haldar MK Mallik S Srivastava DK 《Journal of the American Chemical Society》2004,126(41):13206-13207
The enzyme inhibitors are usually designed by taking into consideration the overall dimensions of the enzyme's active site pockets. This conventional approach often fails to produce desirable affinities of inhibitors for their cognate enzymes. To circumvent such constraints, we contemplated enhancing the binding affinities of inhibitors by attaching tether groups, which would interact with the surface exposed amino acid residues. This strategy has been tested for the inhibition of human carbonic anhydrase II. Benzenesulfonamide serves as a weak inhibitor for the enzyme, but when it is conjugated to iminodiacetate-Cu2+ (which interacts with the surface-exposed His residues) via a spacer group, its binding affinity is enhanced by about 2 orders of magnitude. This "two-prong" approach is expected to serve as a general strategy for converting weak inhibitors of enzymes into tight-binding inhibitors. 相似文献
136.
A finite state stationary process is defined to be loosely block independent if long blocks are almost independent in the
sense. We show that loose block independence is preserved under Kakutani equivalence and
limits. We show directly that any loosely block independent process is the
limit of Bernoulli processes and is a factor of a process which is Kakutani equivalent to a Bernoulli shift. The existing
equivalence theory then yields that the loosely block independent processes are exactly the loosely Bernoulli (or finitely
fixed) processes. 相似文献
137.
138.
Homer RW Swanson J Jilek RJ Hurst T Clark RD 《Journal of chemical information and modeling》2008,48(12):2294-2307
SYBYL line notation (SLN) is a powerful way to represent molecular structures, reactions, libraries of structures, molecular fragments, formulations, molecular queries, and reaction queries. Nearly any chemical structure imaginable, including macromolecules, pharmaceuticals, catalysts, and even combinatorial libraries can be represented as an SLN string. The language provides a rich syntax for database queries comparable to SMARTS. It provides full Markush, R-Group, reaction, and macro atom capabilities in a single unified notation. It includes the ability to specify 3D conformations and 2D depictions. All the information necessary to recreate the structure in a modeling or drawing package is present in a single, concise string of ASCII characters. This makes SLN ideal for structure communication over global computer networks between applications sitting at remote sites. Unlike SMILES and its derivatives, SLN accomplishes this within a single unified syntax. Structures, queries, compounds, reactions, and virtual libraries can all be represented in a single notation. 相似文献
139.
140.
There is increasing use of joined ceramic and metallic material combinations exposed to a widening range of temperature. However, difficulties arise from the interaction of the different thermal expansion and ductility properties of component materials when a brazed joint is cooled from brazing to room temperature. Reliability demands on equipment employing ceramicto-metal bonds in structural and sealing applications justify the efforts made for a more complete understanding of the mechanics invelved. For this investigation, specimens were made by copper brazing the ID of a thin-wall metal ring to the OD of a ceramic disk. Residual stresses were induced as the bond metal solidified at the interface of the ring and disk. Electrical-resistance strain gages were fastened to the OD of the metal ring to determine change in stress as the braze material was removed. An apparatus and technique were developed for chemical removal of the braze material while protecting the specimen materials and instrumentation from corrosion. Stress-strain curves of the metals involved were obtained up to 1500°F. This data was used to predict the magnitude of the stresses. The calculated and measured stresses were in reasonable agreement. 相似文献